CN108232164A - A kind of lithium sulfur battery anode material and preparation method thereof - Google Patents
A kind of lithium sulfur battery anode material and preparation method thereof Download PDFInfo
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- CN108232164A CN108232164A CN201810037845.6A CN201810037845A CN108232164A CN 108232164 A CN108232164 A CN 108232164A CN 201810037845 A CN201810037845 A CN 201810037845A CN 108232164 A CN108232164 A CN 108232164A
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The invention belongs to lithium-sulfur cell Material Fields, specifically disclose a kind of lithium sulfur battery anode material, including host material and the elemental sulfur being supported on host material；The host material includes carbon nanotube and compound transient metal sulfide on the carbon nanotubes.The invention also discloses the preparation method and application of the positive electrode.In the present invention, the strategy of addition transient metal sulfide is taken, reduces shuttle effect；Second, adding in carbon nanotube prevents caving in for electrode structure；The positive electrode has excellent chemical property, applies it in lithium-sulfur cell and shows high initial discharge capacity, high coulombic efficiency and high rate capability.
Description
Technical field
The present invention relates to a kind of lithium sulfur battery anode materials and preparation method thereof, belong to lithium-sulfur cell material preparation technology neck
Domain.
Background technology
Lithium-sulfur cell possesses higher energy density (2600W h kg compared with existing lithium ion battery-1) and specific volume
Measure (1675mA h g-1), and rich reserves of sulphur are cheap and easy to get, and in environmentally friendly, therefore, lithium-sulfur cell is most potential to be become
Energy storage equipment of new generation.Although lithium-sulfur cell has many good qualities, it is commercialized also that there are some challenges.First, sulphur
Poor electric conductivity and discharging product lithium sulfide causes anode utilization rate relatively low.Second, the intermediate product of highly dissoluble (lithium it is more
Sulfide), the immediate loss of active material and unfavorable shuttle effect can be caused.Third, the large volume of sulphur in cyclic process
Expansion (~80%) easily causes caving in for electrode structure.These problems result in the low specific capacity of lithium-sulfur cell, capacity it is quick
Attenuation and low coulombic efficiency.
In recent years, people are dedicated to design synthesis carbon-based material, soon to promote the performance of lithium sulfur battery anode material
The electronics transfer of speed can effectively inhibit the shuttle effect of polysulfide.These carbon-based materials include hollow carbon balls, macropore or mesoporous
Carbon, carbon nanotube and graphene etc..Such as：(Publication No. CN106711427A) such as Lv Wei discloses a kind of lithium-sulfur cell with just
Pole material and its application method, the positive material for lithium-sulfur battery are mainly made of carbon nanotube and polyvinylpyrrolidone,
Structure is the block with lamella and vertical through-hole, and the lamella is mutually parallel with the vertical through-hole, application method
For above-mentioned block is pressed, then immerse in sulphur-containing solution or sulphur-containing solution is added drop-wise to above-mentioned block along the direction of vertical slice
In, then used directly as lithium-sulphur cell positive electrode.The positive electrode can significantly improve the electric conductivity of lithium-sulphur cell positive electrode, show
Writing reduces the shuttle effect of polysulfide, so as to improve the electrochemistry comprehensive performance of lithium-sulfur cell.However, the positive electrode is not
Can effectively capture the lithium of polarity polysulfide and sulphur load capacity it is not high, therefore cannot inherently improve lithium-sulfur cell
Performance.
In addition, some are reported in the prior art using TiO2, MnO2, Ti4O7Report as polysulfide sorbing material
Road.Such as Hwang (High-energy, high-rate, lithium-sulfur batteries：synergetic effect
of hollow TiO2-webbed carbon nanotubes and a dual functional carbon-paper
Interlayer.Adv.Energy Mater.6 (2016) 1501480.) design synthesized a kind of lithium sulfur battery anode material, should
Positive electrode is mainly made of sulphur simple substance, hollow mesoporous TiO 2 and carbon nanotube, wherein, sulphur is encapsulated in hollow mesoporous two
In the duct of titanium oxide, the latter is connected with carbon nanotube.Since successfully sulphur is encapsulated in titanium dioxide and electron transfer rate
Raising, which is applied in lithium-sulfur cell to show excellent performance, make battery have high power capacity, and 1C,
Still there is good capacity retention ratio under the high charge-discharge magnification of 2C and 5C.
The electric property of existing lithium sulfur battery anode material, such as initial discharge capacity, high coulombic efficiency and high magnification etc.
There are still larger rooms for promotion for the performance of aspect.
Invention content
The technical issues of electric property to solve existing lithium sulfur battery anode material is undesirable, the present invention provides one kind
Lithium sulfur battery anode material, it is intended to promote the electric property of positive electrode.
Second purpose of the invention is, provides a kind of preparation method of the lithium sulfur battery anode material.
A kind of lithium sulfur battery anode material, including host material and the elemental sulfur being supported on host material；Described
Host material includes carbon nanotube and compound transient metal sulfide on the carbon nanotubes.
Material of the present invention utilizes being total between the active component S in the sulfide and lithium-sulfur cell of transition metal
Valency acts on, and promotes the migration of the electronics between them, improves the charge and discharge electrical property of lithium-sulfur cell, the particularly charge and discharge under high magnification
Electrical property.
In the present invention, the strategy of addition transient metal sulfide is taken, reduces shuttle effect；Second, add in carbon nanotube
Prevent caving in for electrode structure；The positive electrode has excellent chemical property, applies it in lithium-sulfur cell and shows
High initial discharge capacity, high coulombic efficiency and high rate capability.
Technical solution of the present invention using the unique interaction of transition metal sulfide and sulphur simple substance, can obviously reduce
The shuttle effect of polysulfide improves electron transport rate；Make battery that still there is good charge-discharge performance under high magnification.
Preferably, the sulfide of the transition metal includes MoS2、WS2、CrS2、Fe2S3, in CoS, NiS at least
It is a kind of.
Preferably, transient metal sulfide and the mass ratio of carbon nanotube are 1: 5~1: 20；Host material and sulphur simple substance
Mass ratio be 1: 1~1: 4.The electric property of positive electrode under proper ratio is more excellent.
Further preferably, transient metal sulfide and the mass ratio of carbon nanotube are 1: 7~10.
The present invention also provides the preparation method of the lithium sulfur battery anode material, transition metal salt, organic will be included
The solution progress hydro-thermal reaction of sulphur compound, carbon nanotube, obtains host material, sulphur powder is mixed with the host material, with
Afterwards at 100~210 DEG C heat treatment to get the lithium sulfur battery anode material.
The present invention obtains the carbon nanotube that the sulfide of transition metal modifies by hydro-thermal method and is used as the host material of sulphur, then
It is through Overheating Treatment that sulphur powder and the host material is compound up to the lithium sulfur battery anode material.
The transition metal salt can be the water soluble salt for including transition metal cation.
Preferably, the transition metal salt includes ammonium molybdate, ammonium molybdate, ammonium dichromate, ferric sulfate, cobaltous sulfate and sulphur
At least one of sour nickel；Preferably ammonium molybdate and/or ammonium molybdate.
The organic sulfur compound in thiocarbamide, thioacetamide, mercaptoethanol, thioacetic acid, cysteine etc. extremely
Few one kind；It is preferably thiocarbamide and/or thioacetamide.
Preferably, described (whether by transient metal sulfide be revised as transition metal salt) containing transition metal salt is with having
In machine sulfide, the molar ratio of metallic element and element sulphur is 1: 0.5~1: 5；Be conducive to be closed in the range of the amount ratio
The sulfide of conformal looks and size；Preferably it is slightly above the stoichiometric ratio of transition metal and sulphur, such as the chemistry of MoS2 weights Mo and S
Metering is than being 1: 2, using reactant Mo：S is 1: 2~2.5.
The preparation method of the present invention, in advance by transition metal salt and the aqueous solution of organosulfur compound, and the two side is stirred
Mix side mixing；Carbon nanotube is then added again, stirring a period of time, obtains the solution before hydro-thermal reaction.
The transient metal sulfide and the mass ratio of carbon nanotube are 1: 5~1: 20.Mixing time for 4~it is laggard for 24 hours
Row hydro-thermal reaction.Control the amount ratio of carbon nanotube and transient metal sulfide, it is intended to which sulfide is received with carbon in modulate host material
The ratio of mitron is conducive to the host material being had excellent performance under the described conditions；Preferential transient metal sulfide is received with carbon
The mass ratio of mitron is 1: 7~10.
There are larger impact in hydrothermal temperature and time to the pattern of product, structure and performance, the reaction temperature with
It reacts in the range of duration, is conducive to the host material being had excellent performance.Preferably, the hydrothermal temperature for 100~
300℃；Further preferably 160~180 DEG C.Under the preferred range, the performance of obtained product is more excellent.
Preferably, the hydro-thermal reaction time is 6~48h.
Further preferably, the temperature of the hydro-thermal reaction is 180 DEG C, reaction time 12h.
After hydro-thermal reaction, the hydro-thermal reaction solution of gained is filtered, washed, is dried to get the host material.
Preferably, host material and the mass ratio of sulphur simple substance are 1: 1~1: 4.
Sulphur powder and the hybrid mode of host material are preferably ground；The milling time is preferably 5~60min.By sulphur
The mixture of powder and host material is transferred to after stainless steel cauldron increases temperature to 100~210 DEG C first, the retention time 2
~26h.Sulphur is made to diffuse into host material；The mass ratio of sulphur and host material plays an important role to the performance of lithium-sulfur cell, control
Milling time, reaction temperature and reaction time are made, diffusion of the sulphur for being conducive to melt on host material is conducive to promote lithium
The chemical property of sulphur cell positive electrode material.
Preferably, in heat treatment process, first segment heat treatment is carried out at 150~170 DEG C in advance, then 190~210
Second segment heat treatment is carried out at DEG C.In material of the present invention, coordinate the covalent effect of the metal sulfide, cooperation is originally
The heat treatment (sulphur supports) of the preferred two sections of warm areas of invention institute, contributes to the unexpected every electric property for promoting material.
Preferably, the heat preservation heat treatment time being heat-treated in the first segment for 2~for 24 hours；In the second segment
The heat preservation heat treatment time of heat treatment is 0.2~2h.
A kind of preparation method of the preferred lithium sulfur battery anode material of the present invention, includes the following steps：
S1, the aqueous solution for preparing certain density transition transition metal salt and organosulfur compound respectively, and by the two side
Stir side mixing；
S2, a certain amount of carbon nanotube, stirring a period of time are added in into mixed solution obtained by step S1；
S3, step S2 acquired solutions are transferred in stainless steel cauldron, and the stainless steel cauldron is placed on baking
In case, it is maintained at certain temperature for a period of time；
S4, step S3 acquired solutions are filtered, washed, are dried, obtaining host material；
S5, by a certain amount of sulphur powder and the host material mixed grinding for a period of time, and gained mixture is transferred to
In stainless steel cauldron, it is maintained at certain temperature for a period of time, then increases temperature and the short period is maintained to obtain the lithium
Sulphur cell positive electrode material.
The present invention also provides a kind of lithium sulfur battery anode materials, are used to prepare the anode of lithium-sulfur cell.
In the present invention, existing method can be used, anode is assembled into using positive electrode of the present invention.It for example, will packet
Slurry containing the additive (such as bonding agent) for allowing addition in the positive electrode, lithium-sulfur cell coats on a current collector,
Curing obtains the anode.
In the present invention, using existing method, the anode of positive electrode of the present invention will be included, be equipped to lithium sulphur electricity
Pond.
A kind of method that preferred lithium sulfur battery anode material is assembled into lithium-sulfur cell is：By a certain proportion of lithium
Sulphur cell positive electrode material, acetylene black and adhesive (such as PTFE) are mixed and made into 0.2mm thickness, 0.8cm2Disk, then,
It is pressed under 10MPa on the stainless (steel) wire of a diameter 15mm.2025 being assembled in glove box for type button cell operate,
Lithium piece is separated as cathode, centre with Celgard 2300, and electrolyte is the LiTFSi of 1mol/L.Charge-discharge test is using blue electricity
Battery test system (LAND CT2001A).
Preferably, the ratio of the lithium sulfur battery anode material, acetylene black and adhesive (such as PTFE) is respectively
80wt%, 10wt%, 10wt%.
Advantageous effect：
1st, in the lithium sulfur battery anode material of the present invention, place of the carbon nanotube as sulphur of transient metal sulfide modification
Main material, wherein, mainly as carrier and conductive network, metal sulfide is mainly used for acting on polysulfide carbon nanotube.
Metal sulfide, such as MoS2It can be effectively combined, subtract with elemental sulfur and polysulfide with the sulphur on its surface of molybdenum disulfide
Shuttle effect less, and the good contact of electron transport rate carbon nanotube, sulfide and sulphur between them shortens lithium ion
Migration distance accelerates electron transfer speed, can inhibit the polysulfide of lithium diffusion and electric conductivity and machinery it is strong
Degree can improve poorly conductive, volume expansion, active material loss and shuttle effect of sulphur present in current lithium-sulfur cell etc.
Defect, battery performance are increased dramatically.
2nd, lithium sulfur battery anode material of the invention shows high charge-discharge specific capacity and high circulation stability, in 0.2C
Under, beginning discharge capacity is 1473.4mA h g-1, capacity is maintained at 855.2mA h g after 50 cycles-1, coulombic efficiency is up to
96.9%
3rd, lithium sulfur battery anode material preparation flow of the invention is simple, and safety and environmental protection meets requirements of mass production.
Description of the drawings
【Fig. 1】Preparation flow schematic diagram for the present invention；
【Fig. 2】For MoS made from embodiment 12The micromorphology analysis figure of@CNTs-S；Wherein, figure a is MoS2@CNTs'
TEM schemes；Figure b is MoS2The TEM figures of@CNTs-S；MoS can be obtained by scheming a and figure b2@CNTs and MoS2The thickness of@CNTs-S point
Not Wei 23nm and 32nm, the larger thickness of the latter is since sulphur effectively is supported on MoS2On@CNTs；Figure c is spongy MoS2
SEM figure；Figure d is MoS2The SEM figures of@CNTs-S；It is to MoS to scheme e2@CNTs-S carry out the SEM figures in the region of elemental analysis；Figure
F-i is the elemental distribution of corresponding C, O, S and Mo；From may determine that above to the micromorphology analysis of material, MoS2Tightly
It thickly combines on the carbon nanotubes, positive electrode structure during circulating battery can be effectively prevented and caved in；Particularly and S
With reference to, it is effective to reduce shuttle effect, improve electron transport rate；In addition, being uniformly distributed for each element also has ten to battery performance
Divide crucial effect.
【Fig. 3】For MoS made from embodiment 12The XRD and Raman Characterization of@CNTs-S；Wherein, figure a for sulphur simple substance,
MoS2@CNTs-S、MoS2The XRD spectra of@CNTs and CNTs, the diffraction maximum at 2 θ=26.3 ° correspond to carbon nanotube, MoS2@
CNTs has diffraction maximum at 2 θ=13.9 °, 33.3 ° and 59 °, corresponding to MoS2Planar structure, however, in MoS2@CNTs-S
In, since S is in MoS2The covering on surface, it is above-mentioned to correspond to MoS2Diffraction maximum disappear；Figure b is MoS2@CNTs-S and MoS2Drawing
Graceful spectrogram, spongy MoS2Peak value in 244,409 and 809cm-1Place, MoS2@CNTs-S are in 1351cm-1And 1583cm-1Place
Peak correspond to the D bands of carbon nanotube and G bands, 151,216 and 436cm-1The peak at place corresponds to disulfide bond, MoS2@CNTs-S are protected
MoS is stayed2In 809cm-1The peak at place；XRD and Raman spectrum are the result shows that sulphur, MoS2There are strong phases between carbon nanotube
Interaction；Particularly MoS2Between there is S -- S cooperation use.
【Fig. 4】For MoS made from embodiment 12The XPS characterizations of@CNTs-S；Wherein, by figure a it can be seen from material master
Component is wanted as C, Mo, S and O, without other impurities；In addition, the relative intensity of C is weak compared with Mo, illustrate MoS2Effectively modify
On the surface of carbon nanotube；Figure b is high-resolution Mo 3d spectrograms, and 229.07 and 232.9eV corresponds to the Mo 3d of Mo (IV) respectively5/2
S 2s are corresponded to Mo 3d3/2,226.5eV；Figure c is high-resolution S 2p spectrograms, and 162.07 and 163.8eV corresponds to S2 respectively-S
2p1/2and S 2p3/2；Figure d is high-resolution C 1s spectrograms, and 248.8eV confirms the presence of carbon in the material；It is characterized by XPS
It can obtain the MoS2The constituent content of@CNTs-S is：C：41.38%；O：18.2%；S：33.25%：Mo：7.17%.
【Fig. 5】Figure a is MoS2Constant current charge-discharge curve graph of the lithium-sulfur cell that@CNTs-S are assembled under 0.2C；Scheming b is
Charge-discharge performance curve of the battery under 0.2C, initial discharge capacity are 1473.4mA h g-1, hold after 50 cycles
Amount is maintained at 855.2mA h g-1, coulombic efficiency is up to 96.9%；It is by MoS to scheme c2@CNTs-S and CNTs-S (comparative example 2) should
For the charge-discharge performance comparison diagram of battery after lithium-sulfur cell, under 1C, the initial capacity of MoS2@CNTs-S is
1069.4mA h g-1, coulombic efficiency is up to 99.8%, better than CNTs-S；Figure d is MoS2@CNTs-S's and CNTs-S is forthright again
Energy comparison diagram, the former is substantially better than the latter；Figure e is MoS2Charge-discharge performance curves of the@CNTs-S under 2C, initial discharge
Capacity is 996.7mA h g-1, capacity retention ratio is 54.1% after 100 cycles；More than Electrochemical Characterization is forcefully
Illustrate by modifying spongiform MoS on the carbon nanotubes2, the performance of lithium-sulfur cell can be promoted well.
【Fig. 6】For under 1C, MoS2@CNTs-S's (embodiment 1), CNTs-S (comparative example 2) and MoS2-S (comparative example 1)
Charge-discharge performance comparison diagram, MoS2The initial discharge capacity and coulombic efficiency of@CNTs-S is still highest；
【Fig. 7】Scheme the assembling schematic diagram that a is button lithium-sulfur cell；It is by MoS to scheme b, c, d2@CNTs-S and CNTs-S are assembled
Into button lithium-sulfur cell electrochemical impedance spectroscopy, wherein, figure b be battery assemble after stand four days electrochemical impedance spectroscopy,
C is schemed for the just assembled electrochemical impedance spectroscopy of battery, and figure d is the electrochemical impedance spectroscopy after circulating battery 50 times；From above characterization
It can be seen that MoS2For@CNTs-S compared with CNTs-S, the lithium-sulfur cell that the former is assembled into has smaller resistance and faster lithium
Ion diffusion velocity.
Specific embodiment
With reference to specific embodiment, the present invention is further elaborated.Embodiment is interpreted as being merely to illustrate this hair
It is bright rather than limit the scope of the invention.After the content of the invention recorded has been read, based on the principle of the present invention
The various changes or modification made to the present invention equally fall into claims of the present invention limited range.
Embodiment 1
MoS2The preparation of@CNTs-S and its lithium-sulfur cell performance test being assembled into
Step (1)：Carbon nanotube (the MoS of spongiform molybdenum disulfide modification2@CNTs) preparation
S1, respectively by 12mg (NH4)6Mo7O24·4H2O(0.068mmoL；1eqv.) and 12.9mg thiocarbamides (2.5eqv.) are molten
It is mixed while stirring in 25ml pure water, and by the two；
S2,100mg carbon nanotubes are added in into mixed solution obtained by step S1, stirs 12h；
S3, step S2 acquired solutions are transferred in 100ml stainless steel cauldrons, and the stainless steel cauldron is placed
In an oven, 12h is kept at 180 DEG C；
S4, step S3 acquired solutions are filtered, washed, are dried to get the carbon nanometer modified to spongiform molybdenum disulfide
Manage (MoS2@CNTs)；
Step (2)：Carbon nanotube loaded sulphur (the MoS of spongiform molybdenum disulfide modification2@CNTs-S)
By sulphur powder and MoS2@CNTs are transferred to not by 3: 2 quality than one 15min of mixed grinding, and by gained mixture
It becomes rusty in steel reaction kettle, is first maintained at 160 DEG C of 12h, then increase temperature and to 200 DEG C and maintain 20min up to MoS2@CNTs-S。
Step (3)：The assembling of battery and the test of battery performance
By MoS2@CNTs-S, acetylene black and adhesive (such as PTFE) are respectively in the ratio of 80wt%, 10wt%, 10wt%
It is mixed and made into 0.2mm thickness, 0.8cm2Disk, then, the stainless (steel) wire of a diameter 15mm is pressed under 10MPa
On.2025 being assembled in glove box for type button cell operate, and lithium piece is separated as cathode, centre with Celgard 2300, electricity
Solve the LiTFSi that liquid is 1mol/L.Charge-discharge test is using blue electric battery test system (LAND CT2001A).
Embodiment 2
WS2The preparation of@CNTs-S and its lithium-sulfur cell performance test being assembled into
Step (1)：Carbon nanotube (the WS of tungsten disulfide modification2@CNTs) preparation
S1, respectively by 21mg (NH4)10W12O41·xH2O(0.083mmoL；1eqv.) and 15.7mg thiocarbamides (2.5eqv.) are molten
It is mixed while stirring in 50ml pure water, and by the two；
S2,150mg carbon nanotubes are added in into mixed solution obtained by step S1, stirs 8h；
S3, step S2 acquired solutions are transferred in 150ml stainless steel cauldrons, and the stainless steel cauldron is placed
In an oven, 10h is kept at 160 DEG C；
S4, step S3 acquired solutions are filtered, washed, are dried to get the carbon nanotube (WS modified to tungsten disulfide2@
CNTs)；
Step (2)：Carbon nanotube loaded sulphur (the WS that molybdenum disulfide is modified2@CNTs-S)
By sulphur powder and WS2@CNTs are transferred to stainless steel by 3: 2 quality than mixed grinding 20min, and by gained mixture
In reaction kettle, 155 DEG C of 10h are first maintained at, temperature is then increased and to 210 DEG C and maintains 20min up to WS2@CNTs-S。
Step (3)：The assembling of battery and the test of battery performance
By WS2@CNTs-S, acetylene black and adhesive (such as PTFE) are mixed respectively in the ratio of 80wt%, 10wt%, 10wt%
0.2mm thickness, 0.8cm is made in conjunction2Disk, then, be pressed under 10MPa on the stainless (steel) wire of a diameter 15mm.
2025 being assembled in glove box for type button cell operate, and lithium piece is separated as cathode, centre with Celgard 2300, electrolyte
LiTFSi for 1mol/L.Charge-discharge test is using blue electric battery test system (LAND CT2001A).
Comparative example 1
This comparative example is inquired into, and does not use carbon nanotube as structural framing, specific as follows：
Step (1)：Spongiform molybdenum disulfide (MoS2) preparation
S1, respectively by 12.1mg (NH4)6Mo7O24.4H2O and 12.9mg thiocarbamides are dissolved in 25ml pure water, and the two side is stirred
Side mixes；
S2, step S1 acquired solutions are transferred in 100ml stainless steel cauldrons, and the stainless steel cauldron is placed
In an oven, 180 DEG C of 12h are maintained at；
S3, step S2 acquired solutions are filtered, washed, are dried to get to spongiform molybdenum disulfide；
Step (2)：Spongiform molybdenum disulfide sulfur loaded (MoS2)
By sulphur powder and MoS2By 3: 2 quality than mixed grinding 15min, and gained mixture is transferred to stainless steel reaction
In kettle, 155 DEG C of 12h are first maintained at, temperature is then increased and to 200 DEG C and maintains 20min up to MoS2-S。
Step (3)：MoS2The preparation of-S and its lithium-sulfur cell performance test being assembled into：
By MoS2- S, acetylene black and adhesive (such as PTFE) mix system in the ratio of 80wt%, 10wt%, 10wt% respectively
Into 0.2mm thickness, 0.8cm2Disk, then, be pressed under 10MPa on the stainless (steel) wire of a diameter 15mm.2025
Being assembled in glove box for type button cell operates, and lithium piece is separated as cathode, centre with Celgard 2300, and electrolyte is
The LiTFSi of 1mol/L.Charge-discharge test is using blue electric battery test system (LAND CT2001A).
Comparative example 2
The preparation of CNTs-S and its lithium-sulfur cell performance test being assembled into
Step (1)：Carbon nanotube loaded sulphur (CNTs-S)
By sulphur powder and carbon nanotube by 3: 2 quality than one 15min of mixed grinding, and gained mixture is transferred to stainless
In steel reaction kettle, 155 DEG C of 12h are first maintained at, temperature is then increased and to 200 DEG C and maintains 20min up to MoS2-S。
Step (2)：The assembling of battery and the test of battery performance
CNTs-S, acetylene black and adhesive (such as PTFE) are mixed into system in the ratio of 80wt%, 10wt%, 10wt% respectively
Into 0.2mm thickness, 0.8cm2Disk, then, be pressed under 10MPa on the stainless (steel) wire of a diameter 15mm.2025
Being assembled in glove box for type button cell operates, and lithium piece is separated as cathode, centre with Celgard 2300, and electrolyte is
The LiTFSi of 1mol/L.Charge-discharge test is using blue electric battery test system (LAND CT2001A).
Claims (10)
1. a kind of lithium sulfur battery anode material, which is characterized in that including host material and the simple substance being supported on host material
Sulphur；The host material includes carbon nanotube and compound transient metal sulfide on the carbon nanotubes.
2. lithium sulfur battery anode material as described in claim 1, which is characterized in that the transient metal sulfide includes
MoS2、WS2、CrS2、Fe2S3, at least one of CoS, NiS.
3. lithium sulfur battery anode material as claimed in claim 1 or 2, which is characterized in that transient metal sulfide and carbon nanometer
The mass ratio of pipe is 1: 5~1: 20；Host material and the mass ratio of sulphur simple substance are 1: 1~1: 4.
4. such as the preparation method of claims 1 to 3 any one of them lithium sulfur battery anode material, which is characterized in that will include
Transition metal salt, organosulfur compound, carbon nanotube solution carry out hydro-thermal reaction, obtain host material, by sulphur powder with it is described
Host material mixes, and heat treatment is to get the lithium sulfur battery anode material at subsequent 100~210 DEG C.
5. the preparation method of lithium sulfur battery anode material as claimed in claim 4, which is characterized in that the transition metal salt
Including at least one of ammonium molybdate, ammonium tungstate, ammonium dichromate, ferric sulfate, cobaltous sulfate and nickel sulfate；
The organic sulfur compound is at least one of thiocarbamide, thioacetamide, mercaptoethanol, thioacetic acid, cysteine.
6. the preparation method of lithium sulfur battery anode material as claimed in claim 5, which is characterized in that transition metal salt with it is organic
In sulfide, the molar ratio of metallic element and element sulphur is 1: 0.5~1: 5.
7. the preparation method of lithium sulfur battery anode material as claimed in claim 4, which is characterized in that hydrothermal temperature is
100~300 DEG C, the reaction time is 6~48h.
8. the preparation method of lithium sulfur battery anode material as claimed in claim 4, which is characterized in that transient metal sulfide with
The mass ratio of carbon nanotube is 1: 5~1: 20；
Sulphur powder and the hybrid mode of host material are preferably ground, and milling time is preferably 5~60min；
Host material and the mass ratio of sulphur simple substance are 1: 1~1: 4.
9. such as the preparation method of claim 4~8 any one of them lithium sulfur battery anode material, which is characterized in that heat treatment
In the process, first segment heat treatment is carried out at 150~170 DEG C in advance, then second segment heat treatment is carried out at 190~210 DEG C；
Preferably, the heat preservation heat treatment time being heat-treated in the first segment for 2~for 24 hours；It is heat-treated in the second segment
Heat preservation heat treatment time be 0.2~2h.
10. a kind of any one of claims 1 to 3 any one of them lithium sulfur battery anode material or claim 4~9 system
The application of lithium sulfur battery anode material described in Preparation Method, which is characterized in that be used to prepare the anode of lithium-sulfur cell.
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